Process for the polymerization of perfluoroalkyl substituted triazines and products thereof in the presence of ultraviolet radiation



United States Patent 01 iice PROCESS FOR THE POLYMERIZATION OF PER- FLUOROALKYL SUBSTITUTED TRIAZINES AND PRODUCTS THEREOF IN THE PRESENCE OF ULTRAVIOLET RADIATION George A. Grindahl and Ogden R. Pierce, Midland, Mich., assignors to Dow Corning Corporation, Midland, Mich., a corporation of Michigan No Drawing. Application June 12, 1967, Ser. No. 645,523,

now Patent No. 3,453,275, which is a continuation-inpart of application Ser. No. 535,694, Mar. 21, 1966. Divided and this application Feb. 26, 1969, Ser. No.

Int. Cl. C07d 55/50; C08g 33/02 US. Cl. 204-15911 7 Claims ABSTRACT OF THE DISCLOSURE Polymeric triazines are made by condensing bromoor iodo-perfluorotriazines with mercury at temperatures of 30 C. or above, in the presence of ultraviolet light. For example,

('31 f BICFzCFzC CF2CFgBl' was heated at 100 C. and irradiated with ultraviolet light for 16 hours with mercury to give a polymer of the formula CFz Br N N Br CFzOFz CCFaGFz which has excellent thermal and oxidative stability.

SPECIFICATION This application is a divisional of application Ser. No. 645,523, filed June 12, 1967, now US. Pat. 3,453,275, which in turn is a continuation-in-part of application Ser. No. 535,694, filed Mar. 21, 1966, now abandoned.

This application relates to a process for the preparation of polymeric perfluoroalkyl-substituted triazines, which have utility as thermally and oxidatively stable elastomer ingredients, sealants, resins, fibers, films, oils, and coatings. The higher polymeric triazines exhibit excellent solvent resistance.

The process of this application comprises condensing a triazine reactant of the formula by heating it at a temperature of at least 30 C. in the presence of mercury and ultraviolet light where n has a value of at least 1, R is a monovalent fluorocarbon radical of no more than 12 carbon atoms, R is a divalent perfluoroalkylene radical and X is bromine or iodine.

The temperature at which the condensation takes place varies depending on the reaction conditions. When ultraviolet light is employed reaction occurs at 30 C. or above, preferably 50 C. or above. When heat alone is used the Patented Nov. 24, 1970 reaction goes best at C. or above. Of course, the reaction temperature should be below the decomposition temperature of the triazine. In the absence of ultraviolet light the reaction temperature is generally 200 to 300 C. This process can be performed at any pressure and is preferably carried out in an inert atmosphere.

As can be seen from the above formula the starting triazines can contain one or more triazine rings. Thus, where n is 1 the starting material will have the formula but where n is 2, the starting material will have the formula and where n is 4, the formula is It is preferred for R to be difluoromethylene.

The term condensing refers to the fusion of the triazine reactant into a polytriazine of higher molecular weight through the removal of X groups and the reaction of the remaining -R groups with each other to form RR'-- groups.

The main advantage of the process of this application is that it is the first process which can yield purely linear polytriazines when a pure triazine reactant containing two X groups per molecule is used. These materials have greatly improved handling properties over crosslinked polytriazines.

When a branched chain polymer or a polymer of limited molecular weight is required, the above triazine reactant can be cocondensed with a minor amount, usually no more than 20 mol percent, of one or more triazine compounds of either the formula or the formula where R, R, and X are as defined above. Compounds of the first formula serve to terminate the polymerization at the point where it reacts, while compounds of the second formula serve as chain-branching units.

The process of this application therefore provides polytriazines of predictable and controllable structure.

The monotriazines used herein can be prepared from nitriles of the formula NCR'X and NCR, where R, R, and X are defined above, by reacting them under pressure at a temperature of about 150 C. in the presence of silver oxide, HCl, or tetraphenyl tin. When the reaction mixture contains two molar parts of NCR'X and one molar part of NCR, the major product will be F X11 6 JRX which can be purified by distillation.

Other triazines which are useful in the process of this application can be prepared in good yield by altering the proportions of the above nitriles in the reaction mixture.

An alternative method of preparing the monotriazines having one ring is by the series of reactions Iododifluoroacetonitrile and homologues thereof can be prepared in accordance with US. application Ser. No. 467,110, filed June 25, 1965, by William X. Bajzer, now abandoned.

Other nitriles which are represented by the above formulae are known to the art, and methods of their preparation involve known processes and obvious modifications thereof.

The process of this invention results in the production of a bromide or iodide of mercury as a byproduct. The amount of mercury present during the reaction is not critical, but an excess of mercury over the amount required to react with all the bromide or iodine which is present yields the most favorable results.

It is generally not desirable to include diluents such as solvents or oils into the reaction mixture, as the molecular weight of the product is decreased thereby.

NE NH:

The following examples are illustrative only and should not be construed as limiting the invention, which is properly delineated in the appended claims.

EXAMPLE 1 To 20.7 g, (0.051 mole) of .2,4-bis(bromodifiuoromethyl)-6-trifiuoromethy1-1,3,5-triazine, there was added 272.4 g. (1.36 moles) of mercury. This was sealed in a tube under a partial vacuum and heated at 175 C. for 2 hours and at 200 C. for 16 hours while agitating the tube.

The tube was cooled, and the contents were found to have turned into an elastomeric mass.

The product was washed with hexafiuoro-m-xylene, aqueous HCl, diethyl ether, and acetone consecutively. The remaining insoluble product (3.19 g.) was a brown solid which was pliable but nonmelting at temperatures of above to 350 C. yet which exhibited no change after heating in the air for 6 hours at 350 C.

This product was determined to be a polymer of the unit formula having apparently an average of about 350 of such units per molecule and a molecular weight of about 85,000. The determination of the molecular weight was based on a bromine analysis, assuming that the product molecules were bromine-endblocked on each end.

The hexafiuoro-m-xylene wash was evaporated to yield a tan solid (9.1 g.) having a melting range of about to 220 C., and which exhibited fiber-forming properties.

This product was determined to be a mixture of polymers similar to the one above, but of lower molecular weight.

EXAMPLE 2 To 25.23 g. (0.062 mole) of the triazine reactant of Example 1 there was added 330.15 g. (1.645 moles) of mercury. This was heated as in Example 1 at C. for 16 hours. The product was a liquid mixture of the following polymers, dissolved in the remaining triazine monomer, plus the mercury and mercuric bromide byproduct:

where n has a value of 2, 3 and 4. The product were n equals 2 had a melting point of 355 to 36 C.; where n equals 3, the melting point was 70 to 72 C.; and where n equals 4, the melting point was 89 to 90 C., all measured at atmospheric pressure.

Equivalent results can be obtained upon irradiation of the above reaction mixture under a partial vacuum with agitation in a quartz tube with an intense source of ultraviolet light for 48 hours.

EXAMPLE 3 A mixture of 3.16 g. of

l CF15 2 and 13.5 g. of mercury was heated under a nitrogen atmosphere at 330 C. for four hours. A pliable, resinlike,

clear, amber polymer of the above dimer was recovered which showed stability in air at temperatures up to 340 C.

Further heating of the reaction mixture yields rigid polymers of higher molecular weight, particularly when extra mercury is added.

EXAMPLE 4 When 2 molar parts of iododifluoroacetonitrile and one moler part of trifluoroacetonitrile are heated at 150 C. at 10 p.s.i. in the presence of 0.2 molar part of tetraphenyl tin, a triazine of the formula When 2 molar parts of BrCF CF CN and one molar part of C F CN are heated at 175 C. at 100 p.s.i. in the presence of 1 mole of HCl, a liberal yield of (llsFu is formed, as well as smaller yields of When molar parts of (a), 0.1 molar part of (b), and 0.1 molar part of (c) are heated in a bomb for 20 hours at 275 C. with 30 molar parts of mercury, with agitation, a resinous terpolymer of (a), (b), and (c) is formed.

EXAMPLE 6 When 30 molar parts of (llFzcaHs N N Bromol -o Fs/a and 1 molar part of 6 are heated with 65 molar parts of mercury at 250 C. for 24 hours in an agitated bomb, a copolymer of (a) and (b) which is a curable plastic is formed.

where n equals 4, is heated with 20 g. of mercury in a bomb at 300 C., further polymerization takes place, forming polytriazines of higher molecular weight.

Equivalent results are obtained when the reactant is a similar polytriazine where n has an average value of 10 or the reactant is a mixture of polytriazines where n has a value of 35 to 40.

EXAMPLE 8 77.7 g. of bromodifluoroacetonitrile was reacted with 8 g. of ammonia in 200 milliliters of methylene chloride at -75 C. and then warmed to 0 C. to give bromodifluoroacetimidolyl-bromodifiuoroacetamidine IIIH IIIHz (BrCF2( JN=CCF2Br) The solution was then treated at 0 C. with 363.2 g. of perfluorooctanoic anhydride dissolved in milliliters of ether. The acylated imidoylamidine formed a white precipitate. g. of trifluoroacetic anhydride was added at 0 C. and the mixture was warmed to room temperature. The material was extracted with carbon tetrachloride and chromatographic separation of the extract gave 2,4 bis(bromodifluoromethyl) 6 perfluoroheptyl-1,3,5- triazine '1 rr o N N boiling point 230 C., d 1.964 and n 1.3713.

A mixture of 20 g. of this product and g. of Hg was heated at 200 C. for 16 hours. Extraction of the residue with a fluorocarbon ether sold under the name FC-75 gave the polymer EXAMPLE 9 Following the procedure of Example 8:

Bromotetrafluoropropionitrile was reacted with ammonia and the product so formed with trifluoroacetic anhydride to give 2,4-bis(B-bromotetrafluoroethyl)-6- trifluoromethyl-1,3,5-triazine CFs boiling point 93 C. at 23 millimeters, n 1.3872.

20 g. of this compound was mixed with 610 g. of Hg and irradiated with ultraviolet light at 100 C. After 72 hours the mixture was cooled, the excess Hg removed a N N Br CFzCFz-( -ONCE: Br

N n EXAMPLE 10 94 g. of bromodifluoroacetonitrile was added over a 30 minute period to 150 milliliters of anhydrous NH The ammonia was allowed to evaporate overnight. The residue was diluted with 400 milliliters of anhydrous methylene chloride and cooled to 70 C. 58 g. of trifiuoroacetonitrile was then added over a period of 1.5 hours and the mixture was warmed slowly to room temperature over a period of 2 hours. The product was then cooled to 10 C. and 86.1 g. of perfiuoroglutaryl chloride was added dropwise over a period of 45 minutes. The mixture became thick so an additional 200 milliliters of methylene chloride was added. Then 160 g. of trifluoroacetic anhydride was added at C. and after warming the mixture was refluxed for one hour. The reaction mixture was filtered and the filtrate was washed twice with ice water and dried over CaSO After removal of the solvent the compound CFa N B1F2CJZ (CF2)3-JJ N N was obtained, boiling point 145 to 147 C./6.5 minutes 11 1.4042.

A mixture of 4.5 g. of this material and 33 g. of Hg was heated 18 hours at 250 C. to give a polymeric material of the formula EXAMPLE 11 59.5 g. of perfluorosebaconitrile NEC(CF CEN was added to 500 milliliters of anhydrous NH at 70 C. The mixture was warmed to -33 C. and the ammonia was allowed to evaporate overnight. The white solid residue was suspended in 1000 milliliters of methylene chloride. After cooling to 0 C. 210 g. of bromodifluoroacetonitrile was added and the mixture stirred for five days. To the resulting solution was added 135 g. of trifiuoroacetic anhydride. The reaction mixture was stirred for seven hours, washed three times with 1000 milliliters portions of ice water and dried over CaSO The solvent was removed and the residue was twice distilled to give the compound boiling point 152 to 154 C. at 1.1 millimeters.

54.7 g. of the material was mixed with 900 g. of Hg 8 and heated in a quartz flask at to C. for 4 hours while subjected to ultraviolet radiation. The excess Hg was decanted and the residue heated to 280 C. to remove remaining Hg and mercury salts. A dark polymeric material was obtained having the formula That which is claimed is: 1. The process comprising condensing a triazine reactant of the formula by heating it at a temperature of at least 30 C. in the presence of mercury while irradiating the triazine with ultraviolet light, where n has a value of at least 1,

R is a monovalent perfiuorohydrocarbon radical of no more than 12 carbon atoms.

R is a divalent perfiuoroalkylene radical, and

X is bromine or iodine.

2. The process of claim 1 where R is difluoromethylene.

3. The process of claim 1 where R is trifluoromethyl.

4. The process of claim 1 where X is bromine.

5. The process of claim 1 where n is l.

6. The process of claim 1 wherein the temperature is at least 50 C.

7. The process of claim 1 where the condensation takes place in the presence of a minor amount of at least one compound selected from the group consisting of where R, R, and X are as defined in claim 1.

References Cited UNITED STATES PATENTS 3,453,275 7/1969 Grindahl et a1.

MURRAY TILLMAN, Primary Examiner R. B. TURER, Assistant Examiner US. Cl. X.R. 

